Method of forming quartz fibers from extruded rods



April 6, 1965 c. POTTER E'rAL 3,177,057

METHOD 0F FORMING QUARTZ FIBERS FROM EXTRUDED RODS Filed Aug. 2. 1961 E; an am ATTORNEYS f thegraw material Vis available.

United States Patent() 3,177,057 METHOD F FORMING QUARTZ FlBERS FROM EXTRUDED RODS Charles Potter, South Orange, and .lohn W. Lindenthal, Hazlet, NJ., assignors to Engelhard Industries, Inc., Newark, NJ., a corporation of Delaware `Filed-Aug. 2, 19`6VlySer. No. 129,502 6 Claims. (Cl. 65--7) This invention relates to a method and apparatus for forming bonded silica rods and for forming quartz fibers.

This is a continuation-in-part application of our copendingapplication Serial No. 850,573, filed November 3, 1959, now abandoned.

In the production of pure silica fibers, it has been proposed to use a pure fused quartz rod to feed the rod through a special type of torch. One suitable apparatus for this purpose is disclosed in C. Potter patent application No. 803,928, filed April 3, 1959and entitled Fiber Forming Torch, nowL U.S. Patent 3,045,278.

' Upto the present time, the manufacture of pure fused quartz fibers has been a diiiicult and expensive operation. The problems associated with the manufacturing of quartz fibers are principally a result of the high melting point of quartz, which is about 1700 or 'l80'0 C., and above 3,000 F. Thus, in making quartz fibers, using the liberforming torch process, fused quartz rodswere initially formedV from the quartz powder or sand form in which This step requires the application of heat to raise the crystalline quartz powder orsand up to its melting point. Thus, in the formation of quartz fibers, the quartz must be raised tothis very high temperature twice. .These two heating steps and the associated manufacturing procedures have made the formation of quartz fibersv both time-consuming and expensive. Further, applicants found this firstheating stepy to raise the quartz powder up toits melting point to', be disadvantageous forthe reason that it burned out the organic binder typically used to form thev .selfsustainingrod upon extrusion, and this .burning out of the .binder resulted in de teriorationand crumbling of the rod. .The result was that there was nosatisfactory rod available rfor the formation of the fibers.

Principal objects Lof vthe present invention are the simplification and reductionin cost Yof processes and apparatus for` forming quartz fibers. 'v

*,In accordance withthe present invention, an ,economical and commercially practicable method is provided for forming quartz fibers which eliminates the ,requirement of the first heating step of the .prior art for-forming the quartz powderv or sand into rods, the method involving combination of stepsof intimately mixing together the powderedpure orrsubstantially pure silica, a liquid binder composition, comprising from about l50 percent by` weight of a binding agent, and an extrudingl agent, extruding the'mixture into a rod and avoiding heating the vrnixtlglre to high temperatures kduring and after the extrudin'g except for a fiber-forming step hereafter described, anddrying the extruded rod either at vroom temperaturek orhat ra relatively low temperature below 1507v C. IThereafter the rod jis passed into a fibenforming torch having an operating temperature above 17,00" C. to forni thetfibers. The method is a considerable improvenient by reason of providing the following: (l) considerable" reduction in the ,cost of manufacture of the quar'tziibers'becauseueliminating the considerable requirements of fuel and the apparatus required forthe firstheating step of rthe prior art; (2) avoids burning out the organic binder withv attendant deterioration and crumbling of the rod and hence the `desired trod is available vfor thesubsequent formation of fibers; and y(3) simplification and efficiency in operation.

3,177,057 Patented Apr. 6, 1965 The fibers are preferably formed by passing the'selfsustaining rod through the aforementioned fiber-forming torch wherein a forceful annular or sleeve-like gas jet at apressure of from l0 to 150 pounds per .square inch is applied onto the molten peripheralsurface ofian end portion of the rod, the rod having been previously heated in the torch toa temperature below its melting .point and the silica at the surface of the end portion of the rod previously melted by application thereto of the torch flame having a temperature above the melting point of the silica. The gas of this annular `or sleeve-like jet is typically air or steam. Sucha fiber-forming operation is disclosed and claimed in previously mentioned co-pending application SerialNo. 803,928, now U.S. Patent 3,045,278.

Formation of the fibers by meansbf this application of the annular or sleeve-like forceful gas jet is preferred for'the reasons: (l) considerably increased rate of production of the fibers is achieved; (2) increased heat transfer eliiciency is achieved; (3) the high velocity gas jet produces an aspirating suction effect in ythe torch, which draws theflarne and combustion yproducts along the quartz rod to keep the molten quartz hot as the fibers are drawn oif; and (4) the fiameand hot combustion products are drawn out of the combustion chamber and away from its wall so that these walls are not heated unduly.

The extruding agent is added t'o the powdered silica either prior to or after the addition ofthe liquid binder composition in awminor amount, preferably from about 0.1-10 percent by Vweight (based on lweight Iof SiO2), which is sufficient to impart extrudabilityto the composition. .Extruding agents which can be employed include alginic acid, sodium alginate, ammonium lalginate, .polyvinyl alcohol. When polyvinyl alcohol is employed as binder, it is unnecessary to add additional extruding agent, provided a suiiicient amount of polyvinyl alcohol is added, as a minor portion of the polyvinylalcohol will also function as the extruding agent. The use of the extruding agent is essential in this invention to achieve good extrusions Lof silica in the form of the rods, the extruding agent serving to lubricate the silica particles to enable the discrete particles to pass or slip by `one another during the extruding operation to form theselfsustaining rod. Theextruding agent is preferably added to the composition when dissolved yin asuitable liquid solvent, for instance an organic liquid solvent, eg. alcohol, glycerine,.ether, CCL, `or water in the caserof polyvinyl alcohol.

The binder composition ofvthis invention comprises broadly from about l-50 weight percent (based on total composition) of a binding agent, in solution in a suitable liquid solvent or dispersed as a colloidal lsuspension in Water inthe case ofcolloidal silica. Examples ofthe binding agent are silica gel or amorphous silica, cellulose acetate, a water-soluble wax, `polyvinyl alcohol or hydrolyzed ethyl silicate. An especially suitable waterfsoluble wax is one marketed under the trademark name ,Carbowax. When using a liquid binder composition containing an organic binding agent, the composition willA broadly comprise from about l-.50 weight percent (based on total composition) of the organic binding agent such as one of the organic binding agents previously disclosed, in solution in organic. liquid -solvent or water, which solvent usually makes up the balance. The preferredproportion of ,organic binding agent will, of course,depend on the particular binding `agent employed. With use of an organic binding composition containing polyvinyl al' colrol as the binder component, this composition Will preferably contain from about l-lO weight k.percentl of the polyvinyl `alcohol in solution in Water, 'the water making up the balance of the composition, i.e. being present in amount from about 99-90 weight percent.

When the orga-nic binder is a water-soluble wax, the'binder wos? composition will preferably contain from about 1 30 weight percent of the water-soluble wax and from about 99-70 weight percent of water. When the organic binder cate, the binder composition will preferably comprise from f about 25-75 weight percent of the ethyl silicate in solution in water, thewater making up the balance, i.e. being` present in amount of fromabout 75-25 weight percent. The

liquid binder composition is preferably added to the powderedsilica in amount of from. about 0.1- weight percent, more preferably'from about 5-10 weight percent (based on weight of SiOg) Inaccordance with fa featured apparatus of this invention, an extruder is provided for forming rods'of .silica powder mixed with the binder composition. In addition, dryingV apparatus is provided for strengthening the ex-v truded rods prior to their application to a quartz rod fiberforming torch. The yrods may be conveyed from the extruder through the drying apparatus to the liber-forming torch by any suitable apparatus, such as a wire conveyor belt, for example. If the drying zone is sufciently long, no external heat is required; with a short drying zone however, supplemental low temperature heating may ad' vantageously be employed.

In accordance with additional features of the invention, the silica is preferably pure or substantially pure crystalline silica, and the binder preferably comprises amorphous silica in colloidal form.

VThefprincipal advantage of the method and apparatus described above lies in the elimination of one of the two heating steps previously required in the formation of quartz fibers. Thus, it is no longer necessary toheat the quartz powder upto the intense heat required to form the silica rods; instead the powdered silica is merely bonded to form a relatively low strength rod, which does, however, have sufficient strength for application to a liberforming torch.`

Other objects, features and advantages of the invention following detailed description and from the drawing, in which:

FIG. 1 is a schematic showing of the apparatus in accordance with the rpresent invention, and

FIG. 2 isfan enlarged view of a piece of bonded quartz may be readily apprehended from a consideration of the powder rodwhich was removed from the liber-forming torch after the process was stopped.

Referring to the-drawings, FIG. l shows a heavy collar 12 to which an extruder 14 is secured. The extruder 14 includes a piston 16 and a piston rod 18 inv addition to a main chamber 20. The front of the main chamber 20, is closed by a screw-threaded cap 22. and a die 24. TheY die 24 is threaded into the front of the cap 22 for ease in removal or substitution. VAs the piston rod 18 is slowly advanced by a hydraulic system (not shown), quartz powder together withithe binding agent and a suitable extruding agent is forced through the opening in the die l 24; The resulting rod 26 is slowly advanced by the pressure from the extruding head and by a synchronized wire conveyor belt 28.

In one embodiment of the invention, the diameter of theextruderchamber 20 was approximately equal to one 4 and added to the quartz powder in "the be'aker.

burners 30` and 32 rfor applyingsome heat to the rod 26. Any other suitable apparatus such as a conventional 1nfrared lamp, a vacuum drying apparatus, or arperforate tubeheated with resistance. wires, may befemployed instead of the Bunsen burners.- Extruded' rods which have merely been air-dried have also been employedsuccessfully. Suitable .guides 34 -direct1 the rod 26 from the drying zone into the space between the feed rollers 36 and 33 associated with thefibenforming torch 40.

The liber-forming torch 4i) may take any one of a number of knownV forms. Thus, it may be in'v kone 'of the forms shown in rapplication Serial No. 803,928cited above. Alternatively, commercial metallizing guns of certain recentV designs which are capable of producing temperatures above 170() `or 1890" Grand of'acceptingrod-s'of the proper diameter may be employed. f

A relatively slow feed is employed for the piston rod 18 and also for the extruded rod 26. Thus, for example, with a rod of '0716" diameter, the rate of feed through the fiber-forming torch itwould bein ythe order of about `several feet per hour up toabout l0 to lo' feet per hour. The rate may vary with the diameter ofrod which is used; in general, the weight of quartz liber which is Vformed varies from several ounces to about two pounds per hour.

As mentioned above, the bonded rod is of about the samey consistency and strength as blackboard chalk. It may be readily broken usingtwo -iingers4 of each hand. With reference to FIG. 2, a rod is showuwhichisbroken yat the leftfhand end 34. l The other end i6y was near the `output endof the liber-forming torch when the process A typical extruding batch consisted of 25 grams of Brazilian quartz crystal ground to mesh size, 25

grams pure quartz sand of mesh size, 12 ml. of a water suspension of amorphous silica supplied by Du Pont and known as Ludox AS. In` addition, 1.25 grams of 'alginic acid were added as an extruding agent. With regard to the composition ofther water suspension of amorphous silica,.the silica forms l30 percent by weight of the solution. The particlesv of silica are approximately 15 millimicrons in diameter. i

The designation f-lOO mesh size rorf-14() mesh size means that the powder has passed through a screen of 100 mesh or 140 mesh size, respectively.

The silica powders were weighed out tothe nearest tenth of a gramand placedV in `a 250 ml. .beaken The alginicacid wasv weighed tothe nearest 1/100 of a gram These compounds were mixed by blending the alginatein with a glassrod. Following this operation, the water lsuspension of amorphous silica was added slowly,.one or two cubic centimeters -at a time, ywith each addition being stirred in well before the introduction of additional liquid yuntil the liquidr was uniformly distributed 'and no lumps were present. kThe mixture was then placed in the cylinder of the extruder, andthe cap and die were assembled in place. Pressure was appliedto the piston, and a rod of SG diameter was extruded. When rods were permitted to-dry in the air at room temperature, they couldibeA handled after about'two hours. When drying wasperformedrat 110 C., strength was developed within 30 minutes. By Vthe use of slightly higher temperatures provided by a Bunsen Y burner, continuous processes may be accommodated.

Example II f In accordance with an alternative arrangement, 220 grams of lcrystalline quartz finely ground in a ball millare.

...NT y

.remove some of the moisture.

.added as a binder to impart strength to the extruded rods.

The mass is then subjected to a wedgng operation to Specifically, the plastic mass is repeatedly brought into contact'with material .whichabsorbs the excess surface moisture.

The process was then carried forward through the extruding, drying and fiber-forming processes as discussed above.

.Variants of Examples I and II With regard to the ingredients which are to be extruded, the ksilica powder must be pure or substantially pure in order to produce pure silica fibers. Ground Brazilian quartz crystal is ideal for the purpose, and the quartz powder employed in the process may be entirely derived from this material. It may be initially broken up by a quenching process, and ground into a fine powder in a conventional ball mill. Sufiiciently pure silica powder is available from a vnumber of sources. In addition to the use of powder derived from Brazilian .quartz crystal, high purityV silica sand and flint are available from a number of commercial sources. Ground up fused quartz and other forms of SOZ may also be used either by itself or in any -combination with silica from other sources. When the word silica is employed in the present specification and claims, it is understood that all of these forms of silica are included.

-By the term substantially pure silica used herein is meant a high purity silica having a silica content of 96 .percent or higher. rBy the term binding agent used lhereinris meant a material or substance which, when added to the silica prior to extruding same, will function to hold the silica particlesl together after extrusion as a self-sustaining rod. Examples of binding agents suitable for use in this invention have been previously disclosed herein. By the term extruding agent used herein is meant a material or substance which, when added to the silica prior to the extruding step, will serve to lubricate the silica particles sufiiciently to enable the silica particles to pass or slip by one another during the extruding through the die opening in a fashion to form the desired rod extrusion. Examples of suitable extruding agent for use herein are previously disclosed herein.

Concerning the size of the particles in the silica powder which is employed, it is desirable that the powder pass through a 100 mesh screen. Improved results are obtained with finer powder. For example, the finest mesh screens which are commonly made are 325 mesh. Particularly good results were obtained with two samples of silica powder in which 90 percent and 96 percent, respectively, passed through a 325 mesh screen.

With regard to the binding agent, it is desirable to employ either a form of amorphous silica, which will not introduce any significant impurities, or a substance which will burn ofi in the fiber-forming torch. Amorphous silica, or silica gel, in a water ysuspension is to be preferred. It is noted that hydrolyzed ethyl silicate could also be used. In the case of Example II, the iiocculating agent could be ammonium carbonate as well as ammonium nitrate, and a water soluble wax could b 'used as a binder instead of polyvinyl alcohol.

As noted above, 1.25 'grams of alginic acid were added as an extruding agent in Example I. Other extruding agents which could `be employed include sodium alginate, ammonium alginate and polyvinyl alcohol. Other known extruding agents may also be employed. In many cases a separate extruding agent is not required, and the binder or water with which the silica is mixed serves this purpose.

With regard to the proportions of the various ingredients whichmay be used, it may be noted .that Example I disclosed 50 grams of silica powder, 12 milliliters of .liquid binder, and 1.25 grams of an extruding agent.

The percentage of liquid-binder was about 24 percent by weight of the silica powder and the percentage of extruding agent was about 2.5 per cent by weight of the silica powder. When va separate extruding agent is used, yit should generally be in an `amount less than 5 percent of the mixture to be extruded. Using the specific liquid binder mentioned under Example I, the percentage could be variedfrom about fifteen to thirty-five percent. Below ten percent, the mix will not extrude readily, and above thirty-five percent, the mix becomes too liquid to form a self-sustainingrod. With a binder of somewhat lower viscosity, the percentages would be shifted down to` some extent; and with a liquid binder of increased viscosity, somewhat more of the binder would -advantageously be employed. v

In the foregoing examples, reference has been made t0 the use of pure silica to form pure fused silica fibers. In some cases, however, it may be desirable to obtain silica fibers having some impurities. In this regard, it is contemplated that slight additions of other materials which could for exampleform other glassy substances may be employed in the present process. Boric acids, B203, is one such impurity, and itfco'uld be introduced into the mixture to be extruded, as boric acid. The use of .slightly impure silica sand could also produce this result.

It is again noted that a principal advantage of the in- Vention results from the direct formation of pure Silica fibers from crystalline quartz powder' bonded, into a rod. .Through the use of this technique, the silica needube raised to its high melting pointvbut once. Furthermore, this method overcomesthe dual problems of (l) sizing the crystalline quartz for use in afiber-forrning gun and (2) vthe weakness inherent in the discontinuous temperatureexpansion characteristic of crystalline silica.

While the present invention is primarily directed to the production of fused quartz fibers, as noted above, significant impurities or additions may be present in the silica. Under these conditions, the melting point of the bonded rod may be reduced from the 1700 C. to 1800io C. level mentioned above by two or three hundred degrees, for example. In all events, the temperature provided by the fiber-forming torch only needs to be somewhat higher than the melting point of the impure silica.

It is to be understood that the above described arrangements are illustrative of the application of the principles of the invention. Numerous other arrangements may be devised by those skilled in the art without departing from the spirit and scope of the invention.

What is claimed is:

1. A method for forming fused quartz fibers, which comprises mixing together powdered substantially pure silica, from about 0.1-25 weight percent based on the weight of Si02 of a liquid binder composition comprising from about 1-50 weight percent of an organic binding agent, and a minor amount sufiicient to impart extrudability to the resulting mixture of an extruding agent, extruding the mixture into a self-sustaining rod and avoiding heating the mixture to high temperatures sufiiciently high to burn out the organic binding agent during and after the extruding except for a fiber-forming step hereafter described thereby avoiding burning out the organic binding agent from the mixture with attendant deterioration of the rod prior to the fiber-forming, drying the extruded self-sustaining rod at a temperature within the range of from room temperature to up to but below C., and passing the rod into a fiber-forming torch having an operating temperature above 1800 C. thereby forming the fused quartz fibers.

2. A method for forming fused quartz fibers which comprises adding to powdered substantially pure crystal- -linersilica from about 5-10 weight percent 'based on weight of SiO2 of a liquid binder composition comprising from about 1-50 weight percent of an organic binding vagent in solution in from about-99-50weight percent liquid solvent, adding from about 0.1-10 weight percent based on weight of SiO2 of an organic extruding agent to the powdered silica, intimately mixing the powdered silica, binder composition and extruding agent, extruding the mixture into a self-sustaining rod and avoiding heating the mixture to high temperatures suiciently high Vto burn out the organic .binding agent duringy and after the extruding except fora fiber-forming step hereafter described thereby avoiding burning out the organic binding agentl from the mixture with attendant deterioration of the rod prior to-:the fiber forming, drying the extrudedself-sustaining rod at a temperature within the range of from room temperature to up to but below 150 C., and passing the rod through a liber-forming torch havingan operating temperature of above 1800" C. wherein a forcefulsleevelike gas jet at aY pressure of from l() to 150 pounds per square inch is directed from the torch onto the molten peripheral surface of an endr portion of ,the rod, which surface of thelend portion of the rod has been previouslyy heated in the torch to a temperature above its melting point by application of ythe torch. flame thereto to melt the silica at the surface of the rod end portion, thereby forming the fused quartz fibers.

3. A method in accordance with claim 2 wherein the .cent ycellulose acetate insolution in from about 99-75 weight percent of an organic liquid solvent therefor.

6. A method forl forming fused quartz fibers, which 8 comprises mixing ltogether powdered substantially pure crystalline silicaand water to form a suspension, adding to the suspension fromfabout 0.1-5 lweight percent based on SiOZ of a liquid binder compositioncornprising from about v.1 25 weight percent of an organic binding agent, adding from about 0.1-5 weight percent based on Si02 of an organic extruding agent to the suspension, adding a flocculating agent to the suspension to change the suspension to a plasticrnass, extruding the plastic mass to form a self-,sustaining rod and avoiding heating the mass to high temperature sufciently high to burn out the organic binding agent during and after the extruding except for a fiber-forming step hereafter described thereby avoiding burning out the organic binding agent fromV the mixture with attendant deterioration of the rod prior to the iiber forming, drying the extruded rod at a temperature within the range of from room temperature to up togbut below 150 C.,and passing thefrod through a fiber-forming torch having an operating temperature of above' l800 C. wherein a forceful sleeve-like' gas jetat a pressure of Y from l0 to 150 pounds per square inch is directed from the torch onto the molten peripheral surface of an end `portion of the rod, which surface of the end portion of the rod has been previously heated inthe torch to a temperature above its melting y.point by application of the torch iame thereto to melt the silica at the rod end p0rtion, thereby forming the fused quartz fibers.

References Cited lby the Examiner UNlTED STATES lATENTS 2,566,252 v 8/51 v Tooley et al. 65-227 2,724,866 1l/55 Stephens 65-7 2,822,579 2/,58 Silverman 65-7 2,838,882 6/58 Silverman 65-7 2,984,868 5/61 Hill 65-7 DGNALL H. :SYLVESTEIL` Primary Examiner. VWLLIAM l. STEPHENSON, Examiner. 

1. A METHOD FOR FORMING FUSED QUARTZ FIBERS, WHICH COMPRISES MIXING TOGETHER POWDERED SUBSTANTIALLY PURE SILICA, FROM ABOUT 0.1-25 WEIGHT PERCENT BASED ON THE WEIGHT OF SIO2 OF A LIQUID BINDER COMPOSITION COMPRISING FROM ABOUT 1-50 WEIGHT PERCENT OF AN ORGANIC BINDING AGENT, AND A MINOR AMOUNT SUFFICIENT TO IMPART EXTRUDABILITY TO THE RESULTING MIXTURE OF AN EXTRUDING AGENT, EXTRUDING THE MIXTURE INTO A SELF-SUSTAINING ROD AND AVOIDING HEATING THE MIXTURE TO HIGH TEMPERATURES SUFFICIENTLY HIGH TO BURN OUT THE ORGANIC BINDING AGENT DURING AN AFTER THE EXTRUDING EXCEPT FOR A FIBER-FORMING STEP HEREAFTER DESCRIBED THREBY AVOIDING BURNING OUT THE ORGANIC BINDING AGENT FROM THE MIXTURE WITH ATTENDANT DETERIORATION OF THE ROD PRIOR TO THE FIBER-FORMING, DRYING THE EXTRUDED SELF-SUSTAINING ROD AT A TEMPERATURE WITHIN THE RANGE OF FROM ROOM TEMPERATURE TO UP TO BUT BELOW 150*C., AND PASSING THE ROD INTO A FIBER-FORMING TORCH HAVING AN OPERATING TEMPERATURE ABOVE 1800*C. THEREBY FORMING THE FUSED QUARTZ FIBERS. 